Sulphonated organic compound



Patented Feb. 8, 1944 SULPHONATED ORGANIC COMPOUND Donald Price, New York, N. Y., and Roland Kapp,

Newark, N. J., assignors to National Oil Products Company, Harrison, N. J., a corporation of New Jersey No Drawing. Application April 3, 1942,

Serial No. 437,522 A Claims. (Cl. 260-400) This invention relates to new sulphonated esters having wetting and detergent properties and to the preparation of such sulphonated esters. The present case is a continuation-in-part of my prior application Serial No. 297,324, filed on September 30, 1939.

It is well known that there is a large supply of saturated fatty acids now on the market. However, since esters formed by the reaction of these acids with saturated alcohols could not readily be sulphonated or otherwise treated to yield surface active agents, these acids have not been used as extensively in the preparation of wetting agents and detergents as might be desired in view of their ready availability. It has been proposed to react saturated fatty acids with allyl alcohol and to sulphonate the allyl esters thus obtained; however, these sulphonated esters have found no extensive use, and are not of commercial importance.

It is accordingly one object of this invention to prepare new sulphonated derivatives of fatty materials.

It is a further object of this invention to prepare novel wetting agents and detergents from saturated fatty acids.

In accordance with this invention, sulphonation products are prepared from esters having the general formula RA Rc wherein:

Esters according to the above formula are, in accordance with this invention, sulphonated to produce surface active agents. For example, the

preferred esters, i. e. those in which Rn denotes a fatty acid radical containing from 10 to 14 carbon atoms, when sulphonated yield products having highly effective detergent and wetting properties. Furthermore, thesulphonated esters derived from fatty acids containing more than 14 carbon atoms have also proved to be effective detergents and textile finishing and softening agents. The preferred embodiment of this invention involves the preparation of the sulphonated derivatives of methallyl esters, since these compounds may be prepared from the readily available methallyl alcohol CH3 CHZZJJT-TCHZOII and possess particularly effective wetting and detergent properties.

As aforementioned, the selection of the radicals RA, RB and R0 must be made in such a manner as to provide an olefinic tertiary carbon atom. Hence, if R0 is to be a hydrogen atom, then both RA and RB must contain a carbon atom to render the double-bonded. C on the left of the double bond a tertiary carbon atom. In the event that Rc contains a carbon atom, then the double-bonded carbon atom to which it is attached will bean olefinic tertiary carbon atom and RA and RB may be either hydrogens or alkyl groups as desired.

In carrying out this invention any alcohol having the general formula in which RA, RB, R0 and RF are as above defined, may be reacted with a fatty substance, the acid radicals of which contain from 6 to 22 carbon atoms. Preferably, methallyl alcohol is employed since this alcohol is readily available and yields esters which upon sulphonation give products having excellent wetting and/ or detergent properties. However, it is to be understood that other alcohols having the above generic formula may also be employed, such as, for example, ethallyl alcohol; 2-methyl crotyl alcohol; 3-methyl-3- butene-l-ol; 4-methyl-4-pentene-1-ol; methyl-3-propene-1-o1; and the like.

The fatty acids with which the alcohols of the above type are reacted in accordance with this invention may be any of the fatty acids containing from 6 to 22 carbon atoms. fatty acid employed ordinarily depends upon the nature of the product it is desired to obtain. Thus,

for example, wetting agents may be most advantageously prepared by reacting an alcohol of the above type with a fatty acid containing from 10 to 14 carbon atoms and sulphonating the ester thus obtained. We have found that lauric acid yields the most effective wetting agents when treated in accordance with the practice of this invention; however, sulphonated capric esters of The particular one of .the above alcohols are also excellent wetting agents. On the other hand, we have found that sulphonated esters of a higher fatty acid such as stearic acid and one of the above alcohols may be used to advantage as detergents. Among the other acids which may be employed in the practice of this invention are caproic acid, caprylic acid, myristic acid, palmitic acid and oleic acid. Instead of the pure acids, there may be employed mixtures containing one or more of the acidscoming within the requirements above set forth, as for instance the mixed fatty acids derived by hydrolysis from the animal and vegetable oils, fats and waxes. In addition to the free fatty acids, derivatives thereof such as glycerides, e. g. coconut oil, capable of reacting with one of the above alcohols to form the desired esters, may be employed. In view of the well known similarity in the physical and chemical properties between fatty acids on the one hand and naphthenic and rosin acids on the other, it is intended to include naphthenic and rosin acids within the term fatty acids."

The reaction of the alcohol with the fatty acid esterification can be brought about at higher temperatures without any catalyst, using pressure, if necessarmtoavoid escape of the volatile reactants. However, any other method of esteri- :fic'ation may be used in order to give the desired productsifor example, a chloride of an alcohol of the above type may be formed and then reacted with a sodium salt of a fatty acid having from 6 to 22 carbon atoms so as to yield the desired ester.

I The esters prepared as above described are then sulphonated in order to produce surface-active agents having desirable properties. The sulphonation may be carried out in any desirable manner, but preferably the ester is treated with a. mixture of acetic anhydride and sulphuric acid, and the solution agitated at moderately low tem peratures. An inert solvent such as ethylene dichloride may also be used. The sulphonated mass may then be dropped into ice water, neutralized, and the sulphonated product recovered in the usual way. In place of sulphuric acid, other sulphonating agents such as oleum and chlorsulphonic acid may be used. It is to be understood that while the products obtained by treating the esters of this invention with sulphonating agents are referred to as "sulphonated esters, the term sulphonated is used in a broad sense and is intended to cover both sulphated and sulphonated esters. In view of the varying conditions under which these esters may be produced and'in view of the difierence in characteristics between these esters, we are not certain as to whether these esters are sulphates, sulphonates or mixtures thereof, and hence we do not wish to confine our invention to the production of any particular one of these modifications. Whatever the nature of the sulphonation products, the sulpho radical is bound in an unusually stable manner, being highly resistant to alkaline hydrolysis; likewise the products exhibit surface activity of a definitely higher order than is usual in sulphated products. These are strong indications that the sulpho group is linked to the compound in the form of a sulphonic group rather than as a sulphuric ester group.

The sulphonated esters of this invention are capable of a wide variety of uses. As above pointed out, the sulphonated esters prepared from fatty acids having from 10 to 14 carbon atoms or their derivatives are excellent detergent and wetting agents, whereas sulphonated esters prepared from the higher fatty acids, e. g. stearic acid, are effective detergents and textile treating agents. We have found that the sulphonated methallyl esters of this invention possess wetting and detergent properties superior to those of the corresponding allyl esters, These sulphonated esters of this invention may also be employed as foaming agents, softening agents and as assistants in the cleaning, finishing and dyeing of textile material.

The following examples are illustrative of this invention; amounts are given in parts by weight.

Example I 100 parts of lauric acid, 216 parts of methallyl alcohol and 1 part of paratoluene sulphonic acid were mixed and refluxed for 6 hours. The excess methallyl alcohol was then removed by distillation and the residue subjected to a vacuum distillation, whereby a product was obtained having a boiling range between about 158 C. and about 176 C. at 10 mm. pressure. This product upon analysis proved to be methallyl laurate.

25 parts of the methallyl laurate prepared as above described were dissolved in 25 parts of acetic anhydride and 25 parts of 100% sulphuric acid were slowly added thereto with agitation, the temperaturebeing maintained below 10 C. The mixture was then permitted to warm to room temperature, ice and butyl alcohol were added and the resulting mixture neutralized. Two layers were formed, an upper butanol solvent layer and a lower aqueous layer. The aqueous layer was drawn off and the butanol solution was then concentrated to a viscous liquid. This liquid was dissolved in methyl ethyl ketone, the insoluble material filtered off and the ketone evaporated. leaving a solid residue consisting of sulphonated methallyl laurate.

Solutions of the sulphonated methallyl laurate in water were prepared and Draves tests were run thereon to determine the wetting properties of the sulphonated laurate. The following table shows the results of these tests:

sulphonated allyl laurate when prepared and tested in the same manner prove to be far inferior to the sulphonated methallyl laurate with respect to both its solubility in water and its wetting properties.

. Example II 86 parts of capric acid, 216 parts of methallyl alcohol and 1 part of paratoluene sulphonic acid were mixed and refluxed for 8 hours. The reaction product was washed with sodium carbonate and water, then dried and vacuum distilled. The distillation yielded a product boiling from about 144 C. to about 152 C. at 15 mm. pressure,

which upon analysis proved to be chiefly methallyl caprate.

25 parts of the methallyl caprate were dissolved in 25 parts of acetic anhydride and 25 parts oi 100% sulphuric acid were added to the mixture with agitation, the temperature being maintained at about C. The mixture was then permitted to warm to room temperature, ice and butyl alcohol were added and themixture neutralized. The butanol solution layer which separated was removed and evaporated. Theresidue from the evaporation was dissolved in acetone, the solution filtered and sulphonated methallyl caprate recovered by evaporation of the acetone. The sulphona-ted methallyl caprate was subjected to the Braves tests and gave results similar to those found for the sulphonated methallyl laurate.

Example III 128 parts of palmitic acid, 360 parts of methallyl alcohol and 2.5 parts of concentrated sul-- sulphuric acid were added thereto with agitation at a temperature of C. The mixture was permitted to stand at 20C. for one hour and was then poured over crushed ice and neutralized with soda. Butyl alcohol was added to the aqueous mass with agitation, the alcohol layer withdrawn, filtered and the sodium salt of sulphonated methallyl palmitate recovered by crystallization.

Example IV 114 parts of stearic acid, 216 parts of methallyl alcohol and 1 part of paratoluene sulphonic acid were mixed and the mixture refluxed for 4 hours. The excess alcohol was removed by distillation, and the residue washed with sodium carbonate and water and then dried. The dry residue was subjected to vacuum distillation, whereby a product boiling between about 176 C. and about 179 C. at 2 mm. pressure and consisting chiefly of methallyl stearate was obtained. This product was sulphonated as described in Example III,

whereby a product having detergent properties was obtained.

Example V 86 partsof caprylic acid, 259 parts of methallyl alcohol and 1.2 parts of paratoluene sulphonic acid were mixed and the-mixture refluxed for 5 Example V! 14.2 parts (1 mol) of a mixture of alli'lic type alcohols of varying configurations, but largely consisting of alcohols containing unsaturated tertiary carbon atoms and having a molecular weight corresponding to molecules containing 9 carbon atoms, were mixed with 20 parts (1 mol) of lauric acid and the mixture was refluxed at 5 about 195 C. for 5 hours. The refluxing device was provided with a trap toprevent the return of water evolved from the reaction mixture and a sufllcient amount of benzene was incorporated in the reaction mixture to partially fill this trap and to flow back therefrom into the reaction mixture so as to be redistllled and to entrain the water split out during the reaction. This benzene was limited in amount so as to avoid undue cooling of the reaction mixture. When the reaction was completed, the mixture was cooled,

dissolved in ether, and washed with successive portions of dilute sodium hydroxide until neutral and then dried over sodium sulphate and filtered.

The filtered reaction mixture containing the 20 lauryl esters of the mixed alcohols was then distilled up to a temperature of 150 C. at 40 m. m.

pressure to remove the unreacted' mixed alcohols.

The residual ester products were in the form of a pale yellow liquid.

6.5 parts of the ester product prepared as just described-10 parts of acetic anhydride and parts of ethylene dichloride were mixed and chilled on an ice bath. 16 parts of 96% sulphuric acid were slowly added with cooling to 30 prevent a rise in temperature of the mixture.

The mixture was allowed to stand for 10 minutes,'after which a sufficient quantity of petroleum etherwas added to effect a separation thereof into a lower layer containing the sulphonation product and an upper solvent layer containing the ethylene dichloride, petroleum ether and impurities. The lower layer was removed, poured onto ice and neutralized with sodium hydroxide to approximate neutrality, after 40 which sodium carbonate was added to completely neutralize the sulphonated material. 100 parts of butanol were added to the neutralized mass, agitated therewith to extract the sulphonated product, and separated. The butanol extract was washed with successive portions of an aqueous salt solution until the sulphonated product was neutral. Thereafter the butanol was distilled of! from the product, leaving behind a clear, light amber, sulphonated material which readily dissolved in water to give clear foaming solutions of good wetting power. Tabulated herewith are results 01' Draves' tests conducted upon solution of this material.

Strength of solution Sinkingtime seconds.. 8.4 11.4 22.5

It will be evident from the above description that this invention provides new sulphonated ester derivatives which, because of their highly valuable properties, will be oi great interest, particularly to those engaged in the manufacture and treating of textiles and similar materials.

We therefore claim:

1. The sulphonation product of an ester having the general formula:

RA R0 C=(BRrOC|-Rn 114 t 15 wherein Rn, R3 and R0 are radicals selected from the group consisting of hydrogen and alkyl groups containing less than 6 carbon atoms, with the proviso that at least one of the doublebonded carbon atoms must be tertiary; Riis an organic linking group; and Rn is a fatty acid residue containing from 6 to 22 carbon atoms.

2. The sulphonation product of an ester having the general formula:

/C=C'R|?OfiRD Ra wherein RA, RB and Re are radicals selected from the group consisting of hydrogen and alkyl groups containing less than 6 carbon atoms, with the proviso that at least one of the doublebonded carbon atoms must be tertiary; Rr is an organic linking group and RD is the fatty residue of lauric acid.

4. The sulphonation product of an ester hav- 7 ing the general formula:

wherein RA, RB and Re are radicals selected from the group consisting of hydrogen and alkyl groups containing less than 6 carbon atoms, with the proviso that at least one of the doublebonded carbon atoms must be tertiary;- Rr is an organic linking group and R1) is the fatty residue of stearic acid.

5. The sulphonation product of an ester having the general formula:

wherein RA, Ra and R are radicals selected from the group consisting of hydrogen and alkyl groups containing less than 6 carbon atoms, with the proviso that at least one of the doublebonded carbon atoms must be tertiary; Re is an organic linking group and RD is the fatty residue of palmitic acid.

6. The sulphonation product of an ester having the general formula:

wherein R and RB are radicals selected from the group consisting of hydrogen and alkyl groups containing less than 6 carbon atoms; R0 is an alkyl group containing less than 6 carbon atoms; RF is an organic linking group and Rn is a fatty acid residue containing from 6 to 22 carbon atoms.

7. The sulphonation product of an ester having the general formula:

wherein Ra and Rs are radicals selected from the group consisting of hydrogen and alkyl groups containing less than 6 carbon atoms; Re is an alkyl group containing less than 6 carbon atoms; Rr is an organic linking group and Ro is a fatty acid residue containing from 10 to 14 carbon atoms.

8. The sulphonation product of an ester having the general formula:

wherein Ru and Rs are radicals selected from the group consisting of hydrogen and alkyl groups containing less than 6 carbon atoms; Re is an alkyl group containing less than 6 carbon atoms; RF is an organic linking group and Ro is the fatty residue of lauric acid.

9. The sulphonation product of an ester having the general formula:

RA R0 c=c :-Rroc-RD R4 wherein RA and Rs are radicals selected from the group consisting of hydrogen and alkyl groups containing less than 6 carbon atoms; Re is an alkyl group containing less than 6 carbon atoms; RF is an organic linking group and Ro is the fatty residue of stearic acid.

10. The sulphonation product of an ester having the general formula:

wherein RA and Rs are radicals selected from the group consisting of hydrogen and alkyl groups containing less than 6 carbon atoms; Re is an alkyl group containing less than 6 carbon atoms; RF is an organic linking group and RD is'the fatty residue of palmitic acid.

11. The sulphonated methallyl ester of a fatty acid containing from 6 to 22 carbon atoms.

12. The sulphonated methallyl ester of a fatty acid containing from 10 to 14 carbon atoms.

13. sulphonated methallyl laurate.

14. sulphonated methallyl palmitate.

15. sulphonated methallyl stearate.

16. A process which comprises sulphonating an ester having the general formula:

wherein RA, RB and R0 are radicals selected from the group consisting of hydrogen and alkyl groups containing less than 6 carbon atoms, with the proviso that at least one of the double-bonded carbon atoms must be tertiary; R1 is an organic linking group containing 1 to 4 carbon atoms and RD is a fatty acid residue containing from 6 to 22 carbon atoms.

17. A process which involves sulphonating an ester having the general formula:

wherein RA, Re and R0 are radicals selected from the group consisting of hydrogen and alkyl groups containing less than 6 carbon atoms, with the proviso that at least one of the double-bonded carbon atoms must be tertiary; Rr is an organic linking group containing 1 to 4 carbon atoms and Rn is a fatty acid residue containing from 10 to 14 carbon atoms.

18. A process which involves sulphonating an ester having the general formula:

wherein RA, RB and Re are radicals selected from the group consisting of hydrogen and alkyl groups containing less than 6 carbon atoms, with the proviso that at least one of the double-bonded carbon atoms must be tertiary; RF is an organic linking group containing 1 to 4 carbon atoms and Rn is the fatty residue of lauric acid.

19. A process which involves sulphonating an ester having the general formula:

wherein Rs, RB and Re are radicals selected from the group consisting of hydrogen and alkyl groups containing less than 6 carbon atoms, with the proviso that at least one of the double-bonded carbon atoms must be tertiary; RF is an organic linking group containing 1 to 4 carbon atoms and Rn is the fatty residue of stearic acid.

20. A process which involves sulphonating an ester having the general formula:

DONALD PRICE. ROLAND KAPP. 

